CN106113738B - Sandwich structure composite material and preparation method thereof - Google Patents
Sandwich structure composite material and preparation method thereof Download PDFInfo
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- CN106113738B CN106113738B CN201610565999.3A CN201610565999A CN106113738B CN 106113738 B CN106113738 B CN 106113738B CN 201610565999 A CN201610565999 A CN 201610565999A CN 106113738 B CN106113738 B CN 106113738B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
- B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/067—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/025—Particulate layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/718—Weight, e.g. weight per square meter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/08—Cars
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses sandwich structure composite materials and preparation method thereof.The composite material includes hollow glass micropearl laminboard layer and the carbon fiber skin layer positioned at the hollow glass micropearl laminboard layer opposing sides；Glass fibre prepreg cloth hot-press solidifying in mold of the hollow glass micropearl laminboard layer that can be laid in plate or curved surface made of hot melt technique forms, and the carbon fibre initial rinse fabric hot-press solidifying in mold of the carbon fiber skin layer that can be laid in plate or curved surface made of hot melt preimpregnated process forms；Method is first to prepare carbon fibre initial rinse fabric, then prepare glass fibre prepreg cloth, and carbon fibre initial rinse fabric is covered in the two sides of glass fibre prepreg cloth, hot-forming.The method of the invention, simple process, easy to operate, at low cost, the interlayer composite material density prepared is low, light-weight, compression strength is high, bending property is excellent, appearance is high-quality.
Description
Technical field
The present invention relates to sandwich structure composite material technical fields, and in particular to one kind containing hollow glass micropearl sandwich and
Sandwich structure composite material of carbon fiber skin and preparation method thereof.
Background technique
Structural member made of two pieces of firm, firm coverings is separated lightweight core, the moment of inertia of structure is increased, obtains
One counter-bending and buckling load resulting structure, referred to as sandwich.Covering is generally continuous fiber reinforced composite materials, main
Tensile stress in the face as caused by moment of flexure, compression and shear stress are born, core is honeycomb, foam of polymers, cork wood etc., it leads
It bears the shear stress generated by cross force and supports covering not loss of stability.By optimizing structure design, sandwich can
To play the effects of mitigating construction weight, increasing the rigidity of structure, raising structural strength.
Although sandwich has very strong demand, but still be not used in that thin-walled is thick widely or three-dimension curved surface structure
In component.This is primarily due to: although 1, honeycomb has very high compression strength, this characteristic is only applicable to a side
To which dictates that honeycomb sandwich construction can only be used in nearly two-dimensional structure.For three-dimensional structure, due to honeycomb unbearable three
The load on direction is tieed up, so can not compete with isotropic material.In addition honeycomb is open architecture, the folder of honeycomb core material
Central layer plate will appear pit, and surface irregularity limits its use in core material.Furthermore needed between honeycomb and covering using
Bond glue film, increase weight, there are the risks of interfacial separation, and in honeycomb core material there is also aperture sections high water absorbing capacity,
Cellular Spread direction has the unfavorable factors such as lower shear strength.2, honeycomb is anisotropy, and the mechanical property of foam is
Isotropism.Under complicated stress, foam is more able to satisfy structure and intensity requirement than honeycomb, and more and more applications are examined
Worry uses foam of polymers to replace honeycomb as core material.But also have its unfavorable factor as alternative materials, need to by covering and
Unicellular foamed plastic cores are separately formed, and are then again bonded them or co-curing is integral.If necessary to thin-walled thickness such as 0.3mm thickness
The intermediate core material with certain curve form is spent, needs that foam board is cut out 0.3mm's or so using complicated mechanical equipment
Sheet material is then heated to softening point or more and is pre-bent so that foam core material and mold shape are coincide, then are answered with the material of covering
It closes, the disadvantage is that production efficiency is low, quality is not easy to guarantee, foam such as PMI, PPSU etc. that this external enwergy bears high temperature hold at high price
It is also a big factor of limitation high-performance foam core material sandwich structure composite material application.3, there is also lack as core material for cork wood
Point, cannot forming thin-walled thickness structure, complicated curved-surface structure component can not be formed.
Summary of the invention
Based on this, the present invention provides a kind of sandwich containing low-density hollow glass bead sandwich and carbon fiber skin
The preparation method of composite material, it is simple process, easy to operate, at low cost, the sandwich structure composite material density prepared is low,
It is light-weight, compression strength is high, bending property is excellent, appearance is high-quality.
The present invention also provides a kind of sandwich structure composite material, density is low, light-weight, compression strength is high, bending property
It is excellent, appearance is high-quality.It can be applied to the field that 3c electronic product, automobile structure etc. have lightweight, slimming demand.
In order to achieve the object of the present invention, the invention adopts the following technical scheme:
A kind of sandwich structure composite material, including hollow glass micropearl laminboard layer and be located at the hollow glass micropearl press from both sides
The carbon fiber skin layer of sandwich layer opposing sides；The hollow glass micropearl laminboard layer made of hot melt technique that can be spread
The glass fibre prepreg cloth hot-press solidifying being placed in the mold of plate or curved surface forms, and the carbon fiber skin layer is by passing through heat
The carbon fibre initial rinse fabric hot-press solidifying that can be laid in the mold of plate or curved surface made of molten method preimpregnated process forms.
The present invention also provides following technical solutions:
A kind of preparation method of sandwich structure composite material, includes the following steps:
Carbon fiber one-way yarn or carbon fiber woven cloth and the first resin matrix are provided, by carbon fiber one-way yarn or carbon fiber
Woven cloth is drawn under pre-set tension effect, and first resin matrix is compounded in carbon fiber one-way yarn or carbon fiber woven cloth
Two sides, form laminboard layer, woven the first resin matrix melt impregnation in carbon fiber one-way yarn or carbon fiber by hot-pressing roller
In cloth, carbon fibre initial rinse fabric is formed；
Glass fabric, hollow glass micropearl and the second resin matrix are provided, institute is added in the hollow glass micropearl
It states in the second resin matrix, is sufficiently mixed, glass fabric is drawn under pre-set tension effect, by second resin matrix
It is compounded in the two sides of glass fabric with the mixture of hollow glass micropearl, forms laminboard layer, by hot-pressing roller by the second resin
The mixture melt impregnation of matrix and hollow glass micropearl forms the glass fibre containing hollow glass micropearl in glass fabric
Prepreg cloth；
Taking at least one layer of glass fibre prepreg cloth is middle layer, and it is pre- that two sides is covered at least one layer of carbon fiber respectively
Cloth is soaked, is layered in plate or curve mold, mold temperature is 100 DEG C -200 DEG C, pressure 0.5Mpa-5Mpa, keeps the temperature 30min-
90min is to get the sandwich structure composite material.
In wherein some embodiments, first resin matrix or second resin matrix include following parts by weight
Component: 100 parts of resin, 5-35 parts of curing agent, 0.1-5 parts of promotor, first resin matrix or the second resin base
The preparation method of body is will be after the above components are mixed in 70 DEG C of -120 DEG C of heating stirrings.
In wherein some embodiments, the resin is bisphenol A-type glycidyl ether type epoxy resin, bisphenol-f type shrink
One of glycerol ether type epoxy resins, phenolic aldehyde based epoxy resin, bimaleimide resin and cyanate ester resin are a variety of mixed
Close object；The curing agent is thermohardening type latent curative, including dicyandiamide and its derivative, organic acid hydrazides, BF3Amine network
Close one of object, diaminomaleonitrile and its derivative, glyoxaline compound or a variety of mixtures；The promotor is
Imidazoles, imidazoles metal salt complex, organic ureas, tertiary amine, arylamine, hydrazides and guanidine one of derivative etc. or a variety of
Mixture.
Preferably, the resin is selected from E-14, E-21, E-20, E44, E51, E54, CYD F-170, CYD F-
180, one or more of CYD F-2004, F-44, F-48, F-51, F54.
Preferably, the curing agent be selected from dicyandiamide and its derivative, succinic acid hydrazides, adipic dihydrazide,
Phthalic acid dihydrazide, salicylic acid hydrazides, succinic acid hydrazides, decanedioic acid hydrazides, two hydrazides of isophthalic acid, P-hydroxybenzoic acid acid
One of hydrazides, phenyl amino propionic acid hydrazides or a variety of mixtures.
Preferably, the promotor is selected from dimethyl benzyl amine, 2,4,6- tri- (dimethylamino methyl) phenol, three
Ethamine, dimethylethanolamine, 2-methylimidazole, 2-ethyl-4-methylimidazole, N- (3,4- dichlorophenyl)-N', N'- bis-
One of methylurea (DCMU), 1 benzyl 2 methyl imidazole or boron trifluoride etherate or a variety of mixtures.
In wherein some embodiments, the hollow glass micropearl is comprised the following components in parts by weight by surface treatment:
100 parts of hollow glass micro-ball, 80-120 parts of solvent, 1-7 parts of silane coupling agent, 0.2-1.2 parts of surfactant, described is hollow
The preparation method of glass microballoon is to obtain mixed liquor for dispersion is stirred after the above components are mixed, which is dried, is obtained
To hollow glass micropearl.
In wherein some embodiments, the particle size range of the hollow glass micropearl is 10 μm~120 μm, median
D50 is 40 μm -65 μm, real density 0.1g/cm3~0.5g/cm3。
In wherein some embodiments, the glass fabric is the electronic-grade glass fiber cloth of plain weave, the electronics
The grammes per square metre of grade fiberglass cloth is 25g/m2-125g/m2, surface is handled using amino silane.
In wherein some embodiments, the grammes per square metre of the carbon fiber one-way yarn or carbon fiber woven cloth is 75g/m2-
220g/m2。
In wherein some embodiments, the content of the second resin matrix is 20%- in the glass fibre prepreg cloth
45%, the content of hollow glass micropearl is 15%-45%, the glass fibre prepreg cloth in the glass fibre prepreg cloth
The content of middle glass fibre is 30%-45%；Glass fibre prepreg cloth hot pressing before in conjunction with carbon fibre initial rinse fabric is solid
Density after change is 0.6g/cm3-0.8g/cm3。
In wherein some embodiments, the content of the first resin matrix is 30%-45% in the carbon fibre initial rinse fabric.
Sandwich structure composite material of the present invention is to synthesize hollow glass micropearl with glass fabric and resin-bonded
Low density glass Fiber prepreg flexible, two sides are covered with carbon fibre initial rinse fabric, low density glass fiber prepreg after being heating and curing
Cloth forms core material, and high-strength carbon fiber prepreg cloth forms covering, forms sandwich structure composite material together.Although core material compares bee
Nest, foam or light wood core weight, but it is more much lower than the density of the resin base fiber reinforced composite material of suitable thickness.In addition interlayer
When composite construction destroys, the junction that position is normally at core material and covering is destroyed, laminboard layer and skinning layer tree are utilized
Aliphatic radical body is consistent or the characteristics of chemical reaction crosslinking curing occurs together during heating that match, and is capable of forming core material and illiteracy
Skin integral structure preferably plays the performance of sandwich material.Core material and covering are all the preimpregnation that very thin thickness can be coated with
Cloth, can apply in the component with complex three-dimensional curved-surface structure and scale of mass production, easy to operate, simple production process,
The sandwich structure composite material prepared is with density is low, light-weight, compression strength is high, bending property is excellent, appearance matter
Measured advantage.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.The present invention can be with many not
With form realize, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes to this
The understanding of the disclosure of invention is more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The preparation method of sandwich structure composite material of the present invention, includes the following steps:
Carbon fiber one-way yarn or carbon fiber woven cloth and the first resin matrix are provided, by carbon fiber one-way yarn or carbon fiber
Woven cloth is drawn under pre-set tension effect, and first resin matrix is compounded in carbon fiber one-way yarn or carbon fiber woven cloth
Two sides, form laminboard layer, woven the first resin matrix melt impregnation in carbon fiber one-way yarn or carbon fiber by hot-pressing roller
In cloth, carbon fibre initial rinse fabric is formed；
Glass fabric, hollow glass micropearl and the second resin matrix are provided, institute is added in the hollow glass micropearl
It states in the second resin matrix, is sufficiently mixed, glass fabric is drawn under pre-set tension effect, by second resin matrix
It is compounded in the two sides of glass fabric with the mixture of hollow glass micropearl, forms laminboard layer, by hot-pressing roller by the second resin
The mixture melt impregnation of matrix and hollow glass micropearl forms the glass fibre containing hollow glass micropearl in glass fabric
Prepreg cloth；
Taking at least one layer of glass fibre prepreg cloth is middle layer, and it is pre- that two sides is covered at least one layer of carbon fiber respectively
Cloth is soaked, is layered in plate or curve mold, mold temperature is 100 DEG C -200 DEG C, pressure 0.5Mpa-5Mpa, keeps the temperature 30min-
90min is to get the sandwich structure composite material.
Wherein, first resin matrix or second resin matrix include the component of following parts by weight: resin 100
Part, 5-35 parts of curing agent, 0.1-5 parts of promotor, the preparation method of first resin matrix or second resin matrix
Being will be after the above components are mixed in 70 DEG C of -120 DEG C of heating stirring.
Wherein, the resin is bisphenol A-type glycidyl ether type epoxy resin, bisphenol-f type glycidyl ether type epoxy tree
One of rouge, phenolic aldehyde based epoxy resin, bimaleimide resin and cyanate ester resin or a variety of mixtures；The solidification
Agent is thermohardening type latent curative, including dicyandiamide and its derivative, organic acid hydrazides, BF3Amine complex, diamino Malaysia
One of nitrile and its derivative, glyoxaline compound or a variety of mixtures；The promotor is imidazoles, imidazoles metal
Salt complex, organic ureas, tertiary amine, arylamine, hydrazides and guanidine one of derivative etc. or a variety of mixtures.
Preferably, the resin be selected from E-14, E-21, E-20, E44, E51, E54, CYDF-170, CYDF-180,
One or more of CYDF-2004, F-44, F-48, F-51, F54.
Preferably, the curing agent be selected from dicyandiamide and its derivative, succinic acid hydrazides, adipic dihydrazide,
Phthalic acid dihydrazide, salicylic acid hydrazides, succinic acid hydrazides, decanedioic acid hydrazides, two hydrazides of isophthalic acid, P-hydroxybenzoic acid acid
One of hydrazides, phenyl amino propionic acid hydrazides or a variety of mixtures.
Preferably, the curing agent is selected from dimethyl benzyl amine, 2,4,6- tri- (dimethylamino methyl) phenol, three
Ethamine, dimethylethanolamine, 2-methylimidazole, 2-ethyl-4-methylimidazole, N- (3,4- dichlorophenyl)-N', N'- bis-
One of methylurea (DCMU), 1 benzyl 2 methyl imidazole or boron trifluoride etherate or a variety of mixtures.
Wherein, the hollow glass micropearl comprises the following components in parts by weight: hollow glass micro-ball by surface treatment
100 parts, 80-120 parts of solvent, 1-7 parts of silane coupling agent, 0.2-1.2 parts of surfactant, the system of the hollow glass micropearl
Preparation Method is to obtain mixed liquor for dispersion is stirred after the above components are mixed, which is dried, it is micro- to obtain hollow glass
Pearl.
Wherein, the particle size range of the hollow glass micropearl is 10 μm~120 μm, and median D50 is 40 μm -65 μm,
Real density is 0.1g/cm3~0.5g/cm3。
Wherein, the glass fabric is the electronic-grade glass fiber cloth of plain weave, the electronic-grade glass fiber cloth
Grammes per square metre is 25g/m2-125g/m2, surface is handled using amino silane.
Wherein, the grammes per square metre of the carbon fiber one-way yarn or carbon fiber woven cloth is 75g/m2-220g/m2。
Wherein, the content of resin is 20%-45%, the glass fibre prepreg cloth in the glass fibre prepreg cloth
The content of middle hollow glass micropearl is 15%-45%, and the content of glass fibre is 30%- in the glass fibre prepreg cloth
45%；Density of the glass fibre prepreg cloth before in conjunction with carbon fibre initial rinse fabric after hot-press solidifying is 0.6g/cm3-
0.8g/cm3。
Wherein, the content of resin is 30%-45% in the carbon fibre initial rinse fabric.
The above method may also is that
The component of following parts by weight is provided: 100 parts of hollow glass micro-ball, 80-120 parts of solvent, 1-7 parts of silane coupling agent,
0.2-1.2 parts of surfactant, it will be stirred dispersion after the above components are mixed, obtain mixed liquor, which is dried, is obtained
To hollow glass micropearl；The drying temperature of mixed liquor is 80 DEG C -120 DEG C；Preferably 100 parts of hollow glass micro-ball, solvent 100
Part, 4 parts of silane coupling agent, 0.8 part of surfactant.The particle size range of hollow glass micropearl is 10 μm~120 μm, median
D50 is 40 μm -65 μm, density 0.1g/cm3~0.5g/cm3。
The component of following parts by weight: 100 parts of resin, 5-35 parts of curing agent, 0.1-5 parts of promotor is provided, by said components
70 DEG C -120 DEG C are mixed and heated to, is uniformly mixed, resin matrix is obtained；Auxiliary agent can also be added in the component such as to disappear
Infusion, diluent, toughener, fire retardant, coupling agent etc. add different according to the difference of the type of resin and application demand
Auxiliary agent.Resin is bisphenol A-type glycidyl ether type epoxy resin, bisphenol-f type glycidyl ether type epoxy resin, phenolic epoxy
One of resin, bimaleimide resin and cyanate ester resin or a variety of mixtures；The curing agent is thermohardening type
Latent curative, including dicyandiamide and its derivative, organic acid hydrazides, BF3Amine complex, diaminomaleonitrile and its derivative
One of object, glyoxaline compound or a variety of mixtures；The promotor be imidazoles, imidazoles metal salt complex,
Organic ureas, tertiary amine, arylamine, hydrazides and guanidine one of derivative etc. or a variety of mixtures.
The grammes per square metre of offer carbon fiber one-way yarn or carbon fiber woven cloth, carbon fiber one-way yarn or carbon fiber woven cloth is 75g/
m2-220g/m2, carbon fiber one-way yarn or carbon fiber woven cloth are drawn under some tension effect, the resin matrix is passed through
Glue spreader is coated in release paper and forms the first resin glue film, and two layers of first resin glue films are laid in carbon fiber one-way yarn respectively
Or the two sides of carbon fiber woven cloth, laminboard layer is formed with carbon fiber one-way yarn or carbon fiber woven cloth, wherein having resin matrix
One facing towards carbon fiber one-way yarn or carbon fiber woven cloth, the hot-pressing roller heated resin base for being 70 DEG C -140 DEG C by temperature
It is pre- to form carbon fiber so that resin matrix melt impregnation in carbon fiber one-way yarn or carbon fiber woven cloth, removes release paper for body
Soak cloth；Also PE film can be sticked on one side in the first resin glue film, the preceding removing in conjunction with carbon fiber one-way yarn or carbon fiber woven cloth
PE film.Wherein, the content control of resin matrix is 30%-45% in carbon fibre initial rinse fabric.
Glass fabric is provided, glass fabric is the electronic-grade glass fiber cloth of plain weave, electronic-grade glass fiber cloth
Grammes per square metre is 25g/m2-125g/m2, surface is handled using amino silane, treated hollow glass micropearl is added and is set
It in aliphatic radical body, is sufficiently mixed, glass fabric is drawn under some tension effect, the second resin matrix and hollow glass is micro-
The mixture of pearl is coated in release paper by glue spreader and forms the second resin glue film, and two layers of second resin glue films are compound in glass
The two sides of glass fiber cloth forms laminboard layer with glass fabric, the hot-pressing roller heated resin base for being 70 DEG C -140 DEG C by temperature
Body, so that the mixture melt impregnation of the second resin matrix and hollow glass micropearl in glass fabric, removes release paper, shape
At the glass fibre prepreg cloth containing hollow glass micropearl.Also PE film can be sticked on one side in the second resin glue film, with glass fibre
Cloth combines preceding removing PE film.The content of resin matrix is controlled in 20%-45%, glass fibre prepreg cloth in glass fibre prepreg cloth
The content that the content of middle hollow glass micropearl controls the glass fibre in 15%-45%, glass fibre prepreg cloth is controlled in 30%-
45%.Density of the glass fibre prepreg cloth before in conjunction with carbon fibre initial rinse fabric after hot-press solidifying is 0.6g/cm3-0.8g/
cm3。
Taking at least one layer of glass fibre prepreg cloth is middle layer, and it is pre- that two sides is covered at least one layer of carbon fiber respectively
Cloth is soaked, is layered in plate or curve mold, mold temperature is 100 DEG C -200 DEG C, pressure 0.5Mpa-5Mpa, and soaking time is
30min-90min.To get the sandwich structure composite material.
The sandwich structure composite material made of the above method, including hollow glass micropearl laminboard layer and be located at the sky
The carbon fiber skin layer of heart glass microballoon laminboard layer opposing sides；The hollow glass micropearl laminboard layer is by passing through hot melt work
The glass fibre prepreg cloth hot-press solidifying that can be laid in the mold of plate or curved surface made of skill forms, and the carbon fiber covers
Carbon fibre initial rinse fabric hot pressing in mold of the cortex that can be laid in plate or curved surface made of hot melt preimpregnated process is consolidated
Change.
Embodiment to further illustrate the technical scheme of the present invention will be passed through below.
Embodiment one
The preparation method of sandwich structure composite material described in the present embodiment, includes the following steps:
There is provided the component of following parts by weight: median D50 is 40 μm, real density 0.1g/cm3~0.5g/cm3Sky
100 parts by weight of heart glass microsphere, 100 parts by weight of alcohol, 4 parts by weight of silane coupling agent, 0.8 parts by weight of fluorocarbon surfactant add
Enter to high speed disperser high speed and stir, mixing speed is 1500 turns/min, obtains mixed liquor；It is dried in 100 DEG C of baking oven
The hollow glass micropearl handled.
There is provided the component of following parts by weight: 70 parts of bisphenol A-type glycidyl ether type epoxy resin E51, bisphenol-f type are shunk
10 parts of 20 parts of glycerol ether type epoxy resins CYDF-170, phenol aldehyde type epoxy resin F51,7 parts of dicy-curing agent, promotor
Said components are mixed and heated to 95 DEG C of temperature by 3 parts of DCMU (N- (3,4- dichlorophenyl)-N', N'- dimethyl urea),
High-speed stirred is uniformly mixed, and obtains the first resin matrix.
There is provided the component of following parts by weight: 60 parts of E51 of bisphenol A-type glycidyl ether type epoxy resin, 20 parts of E20, double
20 parts of phenol F type glycidyl ether type epoxy resin CYDF-180,26 parts of adipic dihydrazide curing agent, promotor 2- methyl miaow
1 part of azoles, said components are mixed and heated to 100 DEG C of temperature, high-speed stirred is uniformly mixed, and obtains the second resin matrix.
T300 3k twill 200g/m is provided2The carbon fiber woven cloth of grammes per square metre acts on carbon fiber woven cloth in some tension
First resin matrix is coated in release paper by glue spreader and forms the first resin glue film, by two layers of first resins by lower extraction
Glue film and carbon fiber one-way yarn or carbon fiber woven cloth form laminboard layer, by hot-pressing roller at a temperature of 90 °C, so that the first tree
Aliphatic radical body melt impregnation removes release paper in carbon fiber one-way yarn or carbon fiber woven cloth, forms carbon fibre initial rinse fabric, the
The content of one resin matrix is 35%；
1080 glass fabrics are provided, hollow glass micropearl is added in the second resin matrix, is sufficiently mixed, by glass fibers
Wei Bu is drawn under some tension effect, by the second resin matrix and hollow glass micropearl mixture by glue spreader be coated in from
The second resin glue film is formed on type paper, two layers of second resin glue films and glass fabric are formed into laminboard layer, is 100 by temperature
DEG C hot-pressing roller formed so that the mixture melt impregnation of the second resin matrix and hollow glass micropearl is in glass fabric
The content of glass fibre prepreg cloth containing hollow glass micropearl, the second resin matrix is 33%, and the content of hollow glass micropearl is
31%, the content of glass fibre is 36%.Glass fibre prepreg cloth is before in conjunction with carbon fibre initial rinse fabric after hot-press solidifying
Density is 0.71g/cm3。
Three layers of above-mentioned glass fibre prepreg cloth are taken, are superimposed together, the opposing sides after overlapping is covered with respectively on one layer
The carbon fibre initial rinse fabric stated, is placed in flat plate mold, is put into that temperature is 150 DEG C, pressure is to keep the temperature in the hot press of 3Mpa
60min is to get sandwich composite board.Sandwich composite board with a thickness of 0.95mm, density 1.11g/cm3.Root
According to 790 standard testing of ASTM, plate bending strength is 1050MPa, bending modulus 60GPa, can replace Mg alloy, magnesium lithium
Alloy is used for lightweight structure.According to application demand, prepreg cloth can also be coated in three-dimension curved surface structure, prepare corresponding three
Tie up complex component.
Sandwich structure composite material obtained by this method, including hollow glass micropearl laminboard layer and two layers of carbon fiber skin
Layer, two layers of carbon fiber skin layer are located at the two sides of hollow glass micropearl laminboard layer.Hollow glass micropearl laminboard layer is by three layers
Glass fibre preimpregnation layer of cloth hot-press solidifying forms, and carbon fiber skin layer is formed by one layer of carbon fibre initial rinse fabric hot-press solidifying respectively.
Embodiment two
The preparation method of sandwich structure composite material described in the present embodiment, includes the following steps:
There is provided the component of following parts by weight: median D50 is 50 μm, real density 0.1g/cm3~0.5g/cm3Sky
100 parts by weight of heart glass microsphere, 100 parts by weight of alcohol, 4 parts by weight of silane coupling agent, 0.8 parts by weight of fluorocarbon surfactant add
Enter to high speed disperser high speed and stir, mixing speed is 1500 turns/min, obtains mixed liquor；It is dried in 100 DEG C of baking oven
The hollow glass micropearl handled.
There is provided the component of following parts by weight: 70 parts of E51 of bisphenol A-type glycidyl ether type epoxy resin, 30 parts of E20, double
Said components are mixed and heated to 90 DEG C of temperature by 8 parts of cyanamide curing agent, 1 part of 2-ethyl-4-methylimidazole, and high-speed stirred is mixed
It closes uniformly, obtains resin matrix, the first resin matrix and the second resin matrix are consistent.
T700 100g/m is provided2The carbon fiber one-way yarn of grammes per square metre, by carbon fiber one-way yarn or carbon fiber woven cloth certain
It is drawn under tension force effect, the first resin matrix is coated in release paper by glue spreader and forms the first resin glue film, by two layers
First resin glue film and carbon fiber one-way yarn or carbon fiber woven cloth form laminboard layer to be made by hot-pressing roller at a temperature of 90 °C
The first resin matrix melt impregnation is obtained in carbon fiber one-way yarn, removes release paper, forms carbon fibre initial rinse fabric, the first resin
The content of matrix is 36%；
1086 glass fabrics are provided, hollow glass micropearl is added in the second resin matrix, is sufficiently mixed, by glass fibers
Wei Bu is drawn under pre-set tension effect, and second resin matrix and hollow glass micropearl mixture are passed through gluing roll coating
The second resin glue film is formed in release paper, and two layers of second resin glue films and glass fabric are formed into laminboard layer, pass through temperature
For 100 DEG C of hot-pressing roller, so that the mixture melt impregnation of the second resin matrix and hollow glass micropearl is in glass fabric,
The glass fibre prepreg cloth containing hollow glass micropearl is formed, wherein the content of the second resin matrix is 31%, hollow glass micropearl
Content be 34%, the content of glass fibre is 35%.The hot pressing before in conjunction with carbon fibre initial rinse fabric of glass fibre prepreg cloth
Density after solidification is 0.8g/cm3。
Two layers of above-mentioned glass fibre prepreg cloth is taken, is superimposed together, the opposing sides after overlapping is covered on two layers respectively
The carbon fiber one-way prepreg cloth stated, two layers of unidirectional prepreg cloth square crossing laying, is placed in flat plate mold, and being put into temperature is 180
DEG C, pressure be 2Mpa hot press in keep the temperature 70min to get sandwich composite board.The thickness of sandwich composite board
For 0.7mm, density 1.25g/cm3.According to 790 standard testing of ASTM, plate bending strength is 1130MPa, and bending modulus is
70GPa, can replace Mg alloy, magnesium lithium alloy, and aluminium alloy is used for lightweight structure.It, can also be by prepreg cloth according to application demand
It is coated in three-dimension curved surface structure, prepares corresponding 3 D complex component.
Sandwich structure composite material obtained by this method, including hollow glass micropearl laminboard layer and two layers of carbon fiber skin
Layer, two layers of carbon fiber skin layer are located at the two sides of hollow glass micropearl laminboard layer.Hollow glass micropearl laminboard layer is by two layers
Glass fibre preimpregnation layer of cloth hot-press solidifying form, carbon fiber skin layer respectively by two layers of unidirectional carbon fibre initial rinse fabric hot-press solidifying and
At.
Embodiment three
The preparation method of sandwich structure composite material described in the present embodiment, includes the following steps:
There is provided the component of following parts by weight: median D50 is 65 μm, density 0.1g/cm3~0.5g/cm3It is hollow
100 parts by weight of glass microsphere, 100 parts by weight of alcohol, 4 parts by weight of silane coupling agent, 0.8 parts by weight of fluorocarbon surfactant are added
It is stirred to high speed disperser high speed, mixing speed is 1500 turns/min, obtains mixed liquor；It is dried in 100 DEG C of baking oven
To the hollow glass micropearl of processing.
There is provided the component of following parts by weight: 50 parts of bisphenol A-type glycidyl ether type epoxy resin E54, bisphenol-f type are shunk
50 parts of glycerol ether type epoxy resins CYDF-180,23 parts of isophthalic dihydrazide curing agent, 2 parts of promotor 2-methylimidazole,
Said components are mixed and heated to 110 DEG C of temperature, high-speed stirred is uniformly mixed, and obtains the first resin matrix.
The component of following parts by weight: 80 parts of bisphenol-f type glycidyl ether type epoxy resin CYDF-180, phenolic is provided
20 parts of epoxy resin F54,30 parts of succinic acid hydrazides curing agent, 5 parts of dimethyl benzyl amine promoter, toughener carboxyl end group butyronitrile
Said components are mixed and heated to 85 DEG C of temperature by 2 parts of rubber (CTBN), and high-speed stirred is uniformly mixed, and obtains the second resin base
Body.
T400 150g/m is provided2The carbon fiber plain weave cloth of grammes per square metre is drawn under some tension effect, by the first resin
Matrix is coated in release paper by glue spreader and forms the first resin glue film, by two layers of first resin glue films and carbon fiber woven cloth
Laminboard layer is formed, by hot-pressing roller at a temperature of 90 °C, so that the first resin matrix melt impregnation removes in carbon fiber woven cloth
Release paper is gone, carbon fibre initial rinse fabric is formed, the content of the first resin matrix is 40%；
2116 glass fabrics are provided, hollow glass micropearl is added in the second resin matrix, is sufficiently mixed, by glass fibers
Wei Bu is drawn under pre-set tension effect, and second resin matrix and hollow glass micropearl mixture are passed through gluing roll coating
The second resin glue film is formed in release paper, and two layers of second resin glue films and glass fabric are formed into laminboard layer, pass through temperature
For 100 DEG C of hot-pressing roller, so that the mixture melt impregnation of the second resin matrix and hollow glass micropearl is in glass fabric,
The glass fibre prepreg cloth containing hollow glass micropearl is formed, wherein the content of the second resin matrix is 35%, hollow glass micropearl
Content be 28%, the content of glass fibre is 37%.The hot pressing before in conjunction with carbon fibre initial rinse fabric of glass fibre prepreg cloth
Density after solidification is 0.79g/cm3。
Take 5 layers of above-mentioned glass fibre prepreg cloth, be superimposed together, the opposing sides after overlapping be covered with respectively two layers it is above-mentioned
Carbon fiber woven cloth, be placed in flat plate mold, be put into that temperature is 160 DEG C, pressure is to keep the temperature 90min in the hot press of 4Mpa,
Up to sandwich composite board.Obtained sandwich composite board with a thickness of 1.4mm, density 0.93g/cm3.According to
790 standard testing of ASTM, plate bending strength are 900MPa, bending modulus 45GPa, can replace Mg alloy, magnesium lithium closes
Gold, aluminium alloy are used for lightweight structure.According to application demand, prepreg cloth can also be coated in three-dimension curved surface structure, preparation is corresponding
3 D complex component.Its density is less than water, can be applied to some particular devices waterborne.
Sandwich structure composite material obtained by this method, including hollow glass micropearl laminboard layer and two layers of carbon fiber skin
Layer, two layers of carbon fiber skin layer are located at the two sides of hollow glass micropearl laminboard layer.Hollow glass micropearl laminboard layer is by five layers
Glass fibre preimpregnation layer of cloth hot-press solidifying forms, carbon fiber skin layer respectively by one layer of carbon fiber braiding prepreg cloth hot-press solidifying and
At.
In above-mentioned preparation method, resin, curing agent, promotor constituent content be according to depending on different resins, because
There are many combined methods for resin, and therefore, the amount of curing agent and promotor cannot be enumerated in range one by one, but be all contained in
Within protection scope of the present invention.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of sandwich structure composite material, which comprises the steps of:
Carbon fiber one-way yarn or carbon fiber woven cloth and the first resin matrix are provided, carbon fiber one-way yarn or carbon fiber are woven
Cloth is drawn, and first resin matrix is compounded in the two sides of carbon fiber one-way yarn or carbon fiber woven cloth, forms laminboard layer, is led to
Hot-pressing roller is crossed by the first resin matrix melt impregnation in carbon fiber one-way yarn or carbon fiber woven cloth, forms carbon fibre initial rinse
Cloth；
Glass fabric, hollow glass micropearl and the second resin matrix are provided, the hollow glass micropearl is added described the
It in two resin matrixes, is sufficiently mixed, glass fabric is drawn, by the mixing of second resin matrix and hollow glass micropearl
Object is compounded in the two sides of glass fabric, forms laminboard layer, by hot-pressing roller by the second resin matrix and hollow glass micropearl
Mixture melt impregnation forms the glass fibre prepreg cloth containing hollow glass micropearl in glass fabric；
Taking at least one layer of glass fibre prepreg cloth is middle layer, and two sides is covered at least one layer of carbon fibre initial rinse respectively
Cloth is layered in plate or curve mold, and mold temperature is 100 DEG C -200 DEG C, pressure 0.5Mpa-5Mpa, keeps the temperature 30min-
90min is to get the sandwich structure composite material.
2. the preparation method of sandwich structure composite material according to claim 1, which is characterized in that the first resin base
Body or second resin matrix include the component of following parts by weight: 100 parts of resin, 5-35 parts of curing agent, promotor 0.1-5
Part, the preparation method of first resin matrix or second resin matrix is will be after the above components are mixed at 70 DEG C -120
DEG C heating stirring.
3. the preparation method of sandwich structure composite material according to claim 2, which is characterized in that the resin is bis-phenol
A type glycidyl ether type epoxy resin, bisphenol-f type glycidyl ether type epoxy resin, phenol aldehyde type epoxy resin, bismaleimide
One of polyimide resin and cyanate ester resin or a variety of mixtures；The curing agent is thermohardening type latent curative, including
Dicyandiamide and its derivative, organic acid hydrazides, BF3In amine complex, diaminomaleonitrile and its derivative, glyoxaline compound
One or more mixtures；The promotor is imidazoles, imidazoles metal salt complex, organic ureas, tertiary amine, virtue
One of derivative of amine, hydrazides and guanidine or a variety of mixtures.
4. the preparation method of sandwich structure composite material according to claim 1, which is characterized in that the hollow glass is micro-
Pearl comprises the following components in parts by weight: 100 parts of hollow glass micro-ball, 80-120 parts of solvent, silane coupling agent by surface treatment
1-7 parts, 0.2-1.2 parts of surfactant；The preparation method of the hollow glass micropearl is to carry out after the above components are mixed
It is dispersed with stirring, obtains mixed liquor, which is dried, hollow glass micropearl is obtained.
5. the preparation method of sandwich structure composite material according to claim 1 or 4, which is characterized in that the hollow glass
The particle size range of glass microballon is 10 μm~120 μm, and median D50 is 40 μm -65 μm, real density 0.1g/cm3~0.5g/
cm3。
6. the preparation method of sandwich structure composite material according to claim 1, which is characterized in that the glass fibre
Cloth is the electronic-grade glass fiber cloth of plain weave, and the grammes per square metre of the electronic-grade glass fiber cloth is 25g/m2-125g/m2, surface uses
Amino silane is handled.
7. the preparation method of sandwich structure composite material according to claim 1, which is characterized in that the carbon fiber list
It is 75g/m to the grammes per square metre of yarn or carbon fiber woven cloth2-220g/m2。
8. the preparation method of sandwich structure composite material according to claim 1, which is characterized in that the glass fibre
The content of the second resin matrix is 20%-45% in prepreg cloth, and hollow glass micropearl contains in the glass fibre prepreg cloth
Amount is 15%-45%, and the content of glass fibre is 30%-45% in the glass fibre prepreg cloth；The glass fibre is pre-
Soaking density of the cloth before in conjunction with carbon fibre initial rinse fabric after hot pressing is 0.6g/cm3-0.8g/cm3。
9. the preparation method of sandwich structure composite material according to claim 1, which is characterized in that the carbon fiber is pre-
The content for soaking the first resin matrix in cloth is 30%-45%.
10. a kind of sandwich structure composite material, which is characterized in that be prepared by the described in any item methods of claim 1-9.
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| CN110561570A (en) * | 2019-09-20 | 2019-12-13 | 中国林业科学研究院木材工业研究所 | Complex bamboo, complex bamboo artificial board and preparation method thereof |
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| CN103287032B (en) * | 2013-06-08 | 2016-05-18 | 浙江华正新材料股份有限公司 | The application of laminated material and preparation method thereof and hollow glass micro-ball |
| CN104356605A (en) * | 2014-12-11 | 2015-02-18 | 哈尔滨广龙通用航空科技有限公司 | Light prepreg for unmanned aerial vehicle shell and preparation method of prepreg |
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